Chemical compositions for general cleaning

ABSTRACT

SOAPED-BASED CLEANING COMPOSITION FOR USE IN HARD OR SOFT WATER, SEA WATER AND BRINE ARE PREPARED BY INCORPORATION INTO OR BLENDING WITH SOAP MINOR QUANTITIES OF OTHER MATERIALS WHICH RENDER THE NATURAL HARDNESS FOUND IN WATER HARMLESS OR EVEN BENEFICIAL TO LAUNDERING AND DISHWASHING PROCESS. THE RAIO OF SOAP TO SYNTHETIC DTERGENT OF THE COMPOSITIONS IS HIGH TO PERMIT THE CLEANING EFFECTIVENESS INHARD OR SOFT WATER, BIODEGRADAILITY, HEALTH HAZARD AND NON-POLLUTING CHARACTER OF THESE COMPOSITIONS TO BE SUBSTANTIALLY THAT OF SOAP WHEN SOAP IS USED IN SOFT WATER. IN ONE EMBODIMENT OF THE INVENTION THE COMPOSITION CONTAINS 90 TO 95 PERCENT OF SOAP AND ABOUT 5 TO 10 PERCENT OF AN ALKYL SULFATE-FREE HIGHER ALCOHOL MIXTURE IN WICH THE FREE HIGHER ALCOHOL CONTENT OF THE MIXTURE IS FROM AOUT 5 TO 15 PERCEENT. ANOTHER EMBODIMENT PROVIDES A COMPOSITION CONTAINING 76-94 PARTS SOAP, 5 TO 10 PARTS ALKYL SULFATE-FREE HIGHER ALCOHOL MIXTURE, 2 TO 4 PARTS OF ANOTHER SYNTHETIC DETERGENT SURFACTANT, 2 TO 8 PARTS OF A SODIUM POLYPHOSPHATE, AND 2 TO 12 PARTS OF AN INORGANIC SALT.

US. Cl. 252-110 8 Claims ABSTRACT OF THE DISCLOSURE Soaped-basedcleaning compositions for use in hard or soft water, sea water and brineare prepared by incorporation into or blending with soap minorquantities of other materials which render the natural hardness found inwater harmless or even beneficial to laundering and dishwashingprocesses. The ratio of soap to synthetic detergent of the compositionsis high to permit the cleaning efiectiveness in hard or soft water,biodegradability, health hazard and non-polluting character of thesecompositions to be substantially that of soap when soap is used in softwater. In one embodiment of the invention the composition contains 90 to95 percent of soap and about to percent of an alkyl sulfate-free higheralcohol mixture in which the free higher alcohol content of the mixtureis from about 5 to percent. Another embodiment provides a compositioncontaining 76-94 parts soap, 5 to 10 parts alkyl sulfate-free higheralcohol mixture, 2 to 4 parts of another synthetic detergent surfactant,2 to 8 parts of a sodium polyphosphate, and 2 to 12 parts of aninorganic salt.

This application is a continuation-in-part of application No. 153,101,filed June 14, 1971, now abandoned.

This invention relates to the preparation of low-cost compositions thatare highly effective in laundering, dishwashing and hard surfacecleaning. The compositions are readily biodegradable and pose no wastedisposal problem in comparison with the presently available commercialpreparations.

Current home laundry processes make use of compositions which mayconsist of detergents, alkali-s, organic and inorganic sequesteringagents mainly phosphates, silicates, carboxymethylcellulose, bleaches,enzymes, optical brighteners and sodium sulfate for cleaning ability.Perfumes, odorants, dyes and dust control agents may also be present toincrease acceptance to the user. Though the cleaning compositionscomprised of the above named ingredicuts are very attractive, thesecompositions have numerous disadvantages. The phosphates, which maycomprise 10 to 40 weight percent of the composition, are a major sourceof water pollution by causing eutrophication of water courses, lakes andother water bodies by fertilization of algae and other undesirable plantlife. Excessive algae and undesirable water plant growth leads tochoking of waterways, malodors and decrease in dissolved oxygen in thewater with consequent depletion of game and edible fish. The water maybecome unfit for human drinking, bathing, cooking, manufacturing andrecreation purposes.

Sodium sulfate and other inorganic salts in the wash eflluent lead toincreased dissolved matter in the watercourse. The optical brightenersand carboxymethylcellulose are substantive to the fabrics of the washload, build United States Patent 0 up with successive washes andcontribute to graying and yellowing. These off-colors are mostnoticeable in White cottons and nylon fabrics. Finely powdered enzymessuch as proteases, lipases and amylases may pose health hazards topersons engaged in their manufacture by breathing of air containingthese enzyme dusts.

The presently used compositions are used in. excessive amounts of 0.5percent by weight in water in accordance with the manufacturers labelrecommendation to use one to one and a half eight ounce cups per washload (usually 12 to 18 gallons of water). Even at these useconcentrations soiled synthetic-fibered materials are not cleaned well.The cuff and neck areas of mens white shirts are also poorly cleaned.

The present day compositions in use are soluble in hard water withoutany visible evidence of lime soap formation such as curds or scum due tothe relative calcium and magnesium insensitivity of the organicdetergents and the water softening ability of the phosphates.

Prior to the use of these phosphate built organic detergent compositionssoap was widely used for laundering. The use of soap required soft wateror lime soaps rings, curds or scum would adhere tenaciously to the wallsof the wash-containing vessel as well as on the fabrics of the washload.

Housewives welcomed the soapless composition, consisting of mainlysynthetic detergents, sequestering phosphates and sodium sulfate, as ananswer to the problems created by the use of soap in hard water.

In soft water soap is a highly effective cleaner of all types of naturaland synthetic fabrics. Many communities are reluctant to invest thecapital required to soften natural water which may contain 100 parts permillion (ppm) calcium and magnesium hardness expressed as equivalentcalcium carbonate to 0 to 50 p.p.m. hardness (considered to besoftwater).

It would be advantageous to be able to use hard water and soap-basedcompositions, if it were possible to render harmless or even beneficialto the wash process the effects of the lime soaps formed during theprocess.

This is made possible in accordance with the first embodiment of thisinvention by providing a composition consisting of a soap, an alkylsulfate and a higher alcohol. When dissolved in 120 F. water of from 0to 300 p.p.m. hardness at a concentration of from 0.1 to 0.3 percent byweight the composition according to my invention meets the requirementsfor furnishing a composition for highly effective laundering in hardwater using soap-based compositions.

The composition of this embodiment of the invention consists essentiallyof about to weight percent of soap and about 5 to 10 weight percent ofan alkyl sulfatefree higher alcohol mixture in which the free higheralcohol content of the alkyl sulfate-free higher alcohol mixture is fromabout 5 to 15 weight percent. The soaps suitable for this compositionare sodium salts of fatty acids which are essentially in the range offrom 8 to 18 carbon atoms, that is, the usual soap-making range. It willbe understood that small amounts of soaps of fatty acids outside thisrange may be present depending upon the source of the fatty acids. Thealkyl sulfate is a sodium alkyl sulfate in which the alkyl portionconsists essentially of alkyl of 8 to 18 carbon atoms. The free alcoholsare monohydric alcohols essentially in the -8 to 18 carbon atom range.The soap, alkyl sulfate and free alcohol may paraffin oxidation, causticfusion, oxo processes and olefin chain growth.

The soap used contributes excellent detergency of soiled cotton andsynthetic fabrics. The sodium alkyl sulfate assists the soap indispersing and emulsifying the lime soap curds formed by the action ofthe calcium and magnesium ions present in hard water on part of thesoap. The high alcohol in combination with the soap and alkyl sulfatepromotes the formation of a stable colloidal dispersion of the limesoaps in the washing medium. This stable state is maintained in even 300p.p.m. hard water and the stable dispersed or emulsified state persistseven during later rinsing operations without formation of lime soapscurds, scum or films on the surface of the washing machine or on thefabrics being washed.

A further unforeseen advantage of this composition is the ability tomaintain a high foam level during the wash or sudsing operation and topermit an immediate cessation of foaming during the rinse operation. Thecomposition is very easily rinsed from the Wash with moderate to lowquantities of water as compared to the quantily of water required torinse out the presently widely used commercial laundry preparations.

The quantity of soap-based composition to be used will vary with thewater hardness increasing from a minimum of 0.1 percent by weight forp.p.m. hard Water to a maximum usage of 0.30 percent by weight for 300p.p.m. hard water.

This level of use of the composition of this invention represents fromabout A to /2 the quantities recommended by manufacturers ofcommercially available compositions.

Among the advantages of the compositions of this invention is theirsuperior cleaning ability. White fabrics after washing have highervisual whiteness, soil removal as observed by removal of gray on nylonand cotton and removal of soil on mens White shirts in the neck andcuifs of sleeves areas is highly effective. Stains such as dried blood,chocolate, milk, tea and coifee stains are more completely removed thanby the largest selling commercial laundry detergents. The washed loadafter drying is odor free, softer and virtually free of lint.

Soap, alkyl sulfate and higher alcohols are among the most easilybiodegraded of organic washing material. They are among the leastirritating to eyes and skin and are among the least toxic ifaccidentally ingested of known cleaning agents. No alkaline builders,phosphates or other cleaning adjuvants are required.

Should the water used be extremely soft a small quantity of hardness maybe introduced to the process water in the wash cycle by addingsufiicient anhydrous calcium chloride to yield about p.p.m. hardness.This hardness in conjunction with the use of the composition of thisinvention promotes free rinsing and rapid removal of persistent orsticky foam in the rinse cycles.

In accordance with a second embodiment of this invention there isprovided another composition, mainly soapbased and containing lesserquantities of lime soap dispersing, stabilizing and free rinse promotingingredients. The use of a soap-based composition containing lesserquantities of synthetic detergent, inorganic sequestrants and inorganicsalts has been found to be a highly effective laundering composition inhard or soft water.

The preferred composition of the second embodiment of the inventionconsists essentially of about 76 to 94 weight percent of a sodium soapderived from fatty acids essentially containing from 8 to 18 carbonatoms, about 2 to 4 weight percent of an anionic, non-ionic oramphoteric detergent selected from the group consisting of alkylsulfates, linear alkyl aryl sulfonates, alkyl sulfonates, alkyl arylpolyether sulfates and sulfonates, alkyl polyether alcohols alkyl arylpolyether alcohols, sorbitol, glycol and glyceryl ester of higher acidsand amine fatty acid condensate amphoterics, 2 to 8 weight percent of asodium salt of phosphoric acid, said sodium salt having sequesteringproperties and being selected from the group consisting of sodiumtripolyphosphate, sodium hexametaphosphate and soidum pyrophosphate, and2.0 to 12 weight percent of an inorganic salt selected from the groupconsisting of sodium chloride and sodium sulfate.

The similarity of the two embodiments lie in their mode of actoin,application and interchangeability. The two embodiments give theformulator a broader selection of ingredients and raw material costs andserve effectively as laundry detergents in automatic laundry machines ofdiffering designs.

Both compositions possess the high cleaning ability of soaps. Thesynthetic detergent present does not exceed about 10 percent by weightof the combined weight of soap and synthetic detergent present. Thus theunique soil suspending property of soap is not impaired by an excessivequantity of synthetic detergent.

During actual washing operation, using home laundry machines, there is asequence of cycles. In the sudsing cycle the washing composition isdissolved in water into which the wash load has been placed. The washingcomposition is dissolved and agitated so as to contact the soiled washload thereby loosening soil from the wash load.

At the conclusion of this sudsing cycle the sudsy water is drained fromthe wash load by gravity, pumping action and centripetal force due tothe spinning of the basket containing the Wash load. Depending on thetexture of the fabrics more or less sudsy solution Will be retained bythe Wash load. Thus heavy cotton beach towels will retain more sudsysolution than dacron shirts.

After draining, a rinsing cycle ensues in which clear water is sprayedon the wash load and said water diluting the sudsy fabric-retained Wateris then eliminated through pores in the wash basket by centripetalforce. Then clear water fills the wash basket and is agitated contactingthe wash load to remove the remaining suds from the wash load. Thesediluted suds are then removed by draining. A sequence of sprays andspins and finally spins to eliminate excessive water from the wash loadterminates the laundry machine washing operation.

The wash load is then dried in a drier; in which operation heated airflowing through the wash load eliminates the moisture retained by theWash load.

Using soap alone as the washing composition various difficulties areencountered. While the cleaning during the suds cycle is highlyeffective, the profuse and dense suds generated by soap may require alonger drainage time to be eliminated during the draining period due tothe sticky character of the soap suds. The suds are also voluminous dueto much entrapped air.

During the rinsing fill with clear hardness-containing water the smallamount of soap suds remaining in the wash load are converted to highlytenacious and sticky lime soap curds. These lime soap curds formed aredue to the reaction of the soap and the hardness (usually calcium andmagnesium salts) of the rinse water. The lime soap curds so formedadhere to the wash load and sides of the wash basket.

The built synthetic detergents in general use also have numerousdisadvantages. The synthetic detergent used being a poor cleaner incomparison to soap must be built or reinforced with corrosion inhibitorssuch as metasilicates, soil suspending agents such as phosphates,antiredeposition agents such as carboxymethylcellulose and excessivequantities of sodium sulfate as a bead forming adjuvant and diluent.Some of these formulations are also highly alkaline thus posing apotential human health hazard to children.

These built compositions tend to clean poorly as compared to soap andwhite fabrics tend to become gray after successive washings. Theaddition of optical brighteners may be required to mask this grayingtendency. The wash load after drying is generally of a stiffer texturethan when washed with soap due to a felting action of the builtcompositions acting on the fabrics of the wash load.

The presence of to 40 percent by weight of phosphates and their disposalalso lead to fertilizing algae and consequent eutrophication of watercourses. The various substitutes, such as NTA and EDTA, proposed toreplace phosphates may also pose a pollution or health hazard. Tartratesand citrates are usually expensive and do not exhibit the desirablethreshold effect of phosphates to be able to peptize soils whenphosphate is present in very small quantities such as 10-20 parts permillion by weight in water.

The compositions of this invention have the high cleaning ability andsoil suspending action of soap. While lime soaps are formed they are notsticky tenacious curds but are formed in an emulsifiable or dispersedstate in which state they can readily be rinsed completely from the washload and sides of the wash basket.

The soap of the compositions of this invention furnishes the highcleaning of the Wash load and the other materials acting in concertmodify the lime soap formed from a bulky, and tenacious curd or scum toa freely rinsable form as well as to improve sudsy water drainage and topromote free rinsing.

In the first embodiment of this invention it was found that the additionof sodium alkyl sulfate and free higher alcohol to soap furnished acomposition which when used as a laundry composition yielded highlyeffective cleaning in hard water. However the proportions used of soap,alcohol and alkyl sulfate are critical.

Preston in U.S. Pat. 2,527,075 also teaches the use of soap, alkylsulfate and free higher alcohol.

However Prestons compositions contain excessive quantities of alkylsulfate and free higher alcohols as compared to the present invention.Preston advocates at least 2 percent by weight free higher alcohol andpreferably 5 percent compared to a maximum of 1.5 percent and preferably0.8 percent in the present invention.

Preston also advocates a 6:1 ratio of soap to synthetic detergent ascompared to 9:1 in the present invention.

Prestons higher synthetic detergent, lower soap and greater free higheralcohol content lead to inferior cleaning, poorer rinsing and a residualhigher alcohol odor as compared to the results yielded by thecomposition of the present invention when both compositions are comparedin use as laundry detergents.

In the second embodiment of this invention the soap serves as the majorcleaning ingredient and the lesser quantities of synthetic detergent,phosphate and salt acting in concert serve to tailor the lime soapformed into an easily rinsable emulsion or dispersion.

The relative proportions of soap, synthetic detergent, phosphate andsalt were found to operate most efficiently within certain limits tooptimize high cleaning, good drainage of suds and free rinsing of limesoaps.

Having established the limits for the first and second embodiments ofthis invention it was found that optimal performing compositions couldbe obtained by blending compositions of the first two embodiments of thepresent invention to give a third embodiment of this invention.

By adding the non-soap ingredients of the first embodiment to thenon-soap ingredients of the second embodiment and then adding thecombined non-soap ingredients to a sodium soap there results a thirdembodiment according to the present invention.

The composition of this third embodiment consist essentially of about 5to 10 parts by Weight of an alkyl sulfate free higher alcohol mixture,about 2 to 4 parts by weight of another synthetic detergent, about 2 to8 parts by weight of a sodium salt of phosphoric acid, about 2 to 12parts by weight of an inorganic salt and about 76 to 94 parts by weightof soap.

The preferred compositions of the three embodiments are those in whichsoap is present at a level of at least 90 weight percent of the combinedsoap, alkyl sulfate and synthetic detergent content.

The use of the soap-based compositions have numerous other advantages.New technology has made available many new synthetic soaps, detergentsand higher alcohols in large volume and at low cost. Many of thesematerials are from new processes and possess unique properties andapplications. Soaps may be derived from naturally occurring fats andoils of a vegetable, marine or animal origin. Soaps may be derived fromhydrogenated fats and oils. Soaps may be derived from the caustic fusionprocess as described in U.S. Pat. No. 3,503,896 from natural orsynthetic alcohols produced by the oxo, and ethylene chain growthprocesses. Soaps may be derived from paraffin oxidation processes aspracticed in the U.S.S.R. and elsewhere. The titre of the acids sprungfrom the soaps by acidifying the soaps and extracting the resultingacids, may be as high as 50 C., the higher titred acids coming fromsoaps operating at optimum detergency at higher wash temperatures. Soapsused may be made from mixed fatty acids having essentially 8 to 18membered carbon chain lengths, with at least about being in the 8 to 18carbon atom range, of alpha branched or unbranched configuration,possessing saturation or unsaturation, of odd or even-membered chainlengths and in all combinations of these properties.

The alkyl sulfate may be made by the sulfation and neutralization ofalcohols or olefins produced from natural occurring fats and oils,produced from the oxo process or by ethylene chain growth processes.Alcohols suitable for use in the compositions of this invention may haveessentially 8 to 18 membered chain lengths, a branched or normalconfiguration, a single hydroxyl group on the primary or secondaryposition, possess saturation or unsaturation, odd or even-membered chainlengths and having these properties in all combination. Mixed alcoholsessentially in the 8 to 18 carbon atoms range are normally used.

The cation of the soap or alkyl sulfate should confer water solubilityto the soap or alkyl sulfate. Sodium is preferred rather than potassiumor amine for reasons of low-polluting and low algae-fertilizing effect.

The higher alcohol may derive from the same processes or sources as thealcohol used to prepare the alkyl sulfate. It may arise from alcoholpresent with the alkyl sulfate due to intentional or unintentionalnon-reaction of the total alcohol in the sulfation process or it may beadded to the fully sulfated alcohol or alkyl sulfate. The free higheralcohol and the alcohol undergoing sulfation may be different incomposition.

The organic detergents of the compositions of this invention may benonionic, anionic or amphoteric. They should be Water soluble or watersolubilizable by the soap of the composition. They should be easily andquickly biodegraded, of a low order of irritation to skin and eyes andbe low cost materials. Some suitable anionic detergents are alkylsulfates, linear alkyl aryl sulfonates, alkyl sulfonates, alkyl arylpolyether sulfates and sulfonates.

Some suitable nonionics for illustrative purposes are alkyl polyetheralcohols, alkyl aryl polyether alcohols, sorbitol, glycol and glycerylesters of higher acids.

Ethoxy adducts may be replaced by propoxy and butoxy products. Suitablea'mphotherics may be derivedfrom the condensation of amines and fattyacids.

Some suitable inorganic sequestrants are the Water solublepolyphosphates, hexametaphosphates and pyrophosphates. The sodium saltsare preferred.

Ethylenediamine tetracetate and nitrilotriacetate also known as EDTA andNTA are not considered entirely suitable because of their presentunclarified health hazard status.

Suitable inorganic salts are sodium and potassium chlorides andsulfates. The sodium salts are preferred.

Other additives such as dyes, odorants, anti-redeposition agents, dustcontrol agents, soap antioxidants, corrosion inhibitors, alkalis andspray drying adjuvants may be added for applications wellknown in thesoap and detergent art to achieve specific effects without departingfrom the spirit of this invention. These additives are to be added inthe minimal quantity required where needed so as to pose no waterpollution problem or human health hazard.

The compositions of this invention also possess advantages in handdishwashing application. 0.1 to 0.2 percent by weight solutions of thecompositions in water are readily soluble from room temperature to 120F., possess high detergency in soilremoval, are mild, function well inhard or soft water are freely rinsed and pose no waste disposal orfoaming problems.

Presently used hand dishwashing commercial preparations are profuse andpersistent sudsers but only fair soil removers. They also contain amidesand amine oxides and are a potential source of nitrogen for algaefertilization. The persistence of their foam has for example been aproblem in the Suffolk County Section of Long Island, in New York State.The efiluent from dishwashing returns to the house water supply systemand provides a source of incoming foaming water.

The compositions of this invention are also highly effective hardsurface cleaners, automobile or car washes, glass and mirror cleaners,and are useful in preparing disinfectants and emulsions.

The addition of suflicient sodium hypochlorite solution to yield 10 to25 parts per million free chlorine in a 0.2% solution of composition inwash water will sanitize or materially reduce the microorganisms presenton the soiled load in laundry or dishwashing applications.

The invention will now be illustrated by means of the followingnon-limitative examples.

EXAMPLE 1 The following four compositions were prepared and compared fortheir lime soap dispersing properties:

Parts by weight The titre of the fatty acids of the tallow soap was 42C. The alkyl group of the sodium alkyl sulfate and the free alcohol weredrived from coconut oil. The composition by carbon number distributionof the alcohol and alkyl groups was Saturated: Percent by weight C 6 C C47 C 17 C16 9 C 5 Unsaturated:

Mono C 9 Unsaturated di C 2 The composition of acids for the tallow soapwas Saturated: Percent by weight C 0.5 C 3.0 C 0.5 C 25.0 C 1.0

Unsaturated c 18.0 C14 1.0 C 3.5 C 47.5

0.2 percent by weight of Compositions A, B and C were prepared in citywater having 100 p.p.m. calcium hardness calculated as CaCO 50 ml. ofeach of the solutions was diluted with 200 ml. of city water andobserved for lime soap formation in glassware.

Composition A yielded a solution having large lime soap curds and theglass could not be rinsed free of lime soap with city water.

Composition B yielded a solution having a slight film of lime soap abovethe solution and was rinsable using large quantities of city water.

Compositions C and D yielded solutions having no film or evidence oflime soap curds and were homogeneous, stable emulsions. The glasscontainers were freely rinsable with city water.

The ratio of free alcohol to alkyl sulfate in the optimum performingcompositions C and D were 8 to 92 and 15 to respectively as compared to2.5 to 97.5 in the poorer lime soap dispersing composition B.

EXAMPLE 2 The following compositions were prepared and tested as inExample 1.

Parts by weight Composition A: Sodium tallow soap Composition B:

Sodium tallow soap 88 Sodium alkyl sulfate (containing 2.5% freealcohol) 12 Composition C:

Sodium tallow soap 88 Sodium tripolyphosphate 12 Composition D:

Sodium tallow soap i 88 Sodium chloride 12 Composition E:

Sodium tallow soap 88 Sodium alkyl sulfate 5 Sodium chloride 7Composition F:

Sodium tallow soap i 88 Sodium alkyl sulfate 5 Sodium tripolyphosphate 7Composition G:

Sodium tallow soap 88 Sodium alkyl sulfate 2 Sodium tripolyphosphate 4Sodium chloride 6 Composition =I-I:

Sodium tallow soap 76 Sodium alkyl sulfate 4 Sodium tripolyphosphate 8Sodium chloride 12 9 Composition I: Parts by weight Sodium tallow soap94 Sodium alkyl sulfate 2 Sodium tripolyphosphate 2 Sodium chloride 20.2 percent by weight of the compositions in 100 p.p.m. hardness citywater were prepared and diluted 1 part by volume with 4 parts by volumeof 100 p.p.m. city water and observed for lime soap separation andrinsability.

A had a heavy floating lime soap curdlike mass clinging to the side ofthe glassware. The lime soap could not be rinsed from the glass waresides.

B had a slight film of lime soap rinsable with much water.

C had a heavy floating lime soap curdlike mass clinging tenaciously tothe sides of the glassware and could not be rinsed from the glasswaresides.

D ditto E had a small amount of floating lime soap scum and was rinsablewith large quantities of water.

F ditto G, H and I no film, scum or curds evident. Glassware was freelyrinsable with a small quantity of water.

Tests made with sodium sulfate indicated that replacement of sodiumchloride by sodium sulfate yielded equivalent results.

EXAMPLE 3 In an automatic home washing machine using composition C ofExample 1 in a powdered form, a 0.2 percent by weight solution wasprepared in 12 gallons of 120 F. city water of 100 p.p.m. hardness. An 8pound load of soiled laundry, consisting of cotton, acrylic, polyesterand nylon fabrics, was added and washed. Observations were madethroughout the wash cycle for ease of solution of the composition,formation of lime soap in the wash water, on the fabrics and on the wallof the washing machine during washing and rinsing cycles. The washedload was dried in an automatic electric clothes dryer and observed forspeed of drying, cleanliness, odor and softness of the dried fabrics.

Similar washes were performed with a leading highfoaming anioniccommercial preparation and with a leading low-foaming nonioniccommercial preparation.

Composition C of Example 1 was readily soluble in the wash water andyielded no lime soap curds or film in the washing or rinsing cycles.Foaming was excellent throughout the sudsing cycle and disappearedcompletely at the onet of the rinse cycle indicating the free rinsingcharacter of the foam of composition C of Example 1. The dried wash wasfree of soil, stains and lint, mens white shirts were totally free ofsoil on the cuff and neck areas, cotton bath towels were soft and allwashed fabrics were odor free. This wash using composition C of Example1 was repeated twenty times over a two month period with the sameresults and with no evidence of lime soap curds on the walls of thewashing machine or on the fabrics.

Both commercial preparations were used at the rate of 8 ouncesavoirdupois per 12 US. gallons of wash water or at a use level of 0.5%by weight. The anionic-based preparation foamed well initially but lostits foaming ability half way through the sudsing cycle. Visualappearance of the wash indicated incomplete removal of soil on the neckand cuff areas of mens white shirts, much linet clung to the fabrics andthe dried fabrics had a harsh feel. White synthetics appeared slightlygray in color. No evidence of lime soaps was noted.

The nonionic-based commercial prepartion performed in a similar fashionto the anionic-based commercial preparation except foaming was lower.

The approximative composition of the anionic high foaming preparationwas Parts by weight Sodium alkyl aryl sulfonate 15 Sodium metasilicate 5Carboxymethylcellulose 1 Sodium tripolyphosphate 30 Optical brightener0.2 Sodium sulfate n Balance to 100 Enzymes were present.

The approximate composition of the nonionic lowfoaming preparation wasParts by weight Alkyl aryl polyether alcohol n ..l... 10 Sodiummetasilicate 5 Carboxymethylcellulose 1 Sodium tripolyphosphate 30Optical brightener 0.2 Sodium sulfate Balance to 100 Enzymes were notpresent.

The washing machine and dryers were 1968 models of the leading sellingbrands in the United States and Canada.

EXAMPLE 4 Using composition G of Example 2 the same results wereobtained as reported for Example 3 (using Composition C of Example 1).

EXAMPLE 5 Washes using the compositions of Example 1 Composition C andExample 2 Composition G were repeated following the procedure of Example3. However 8 fluid ounces of a 5% sodium hypochlorite solution was addedto the wash cycle.

No evidence of any incompatibility of bleaches and compositions werenoted. No lime soap curds were observed. The dried washed fabrics werebright, clean, odor free and soft to touch. Stain removal was excellent.

EXAMPLE 6 The procedures of Examples 1 through 5 were repeated replacingthe sodium tallow soap of the compositions with an equal weight of asodium soap made from tallow and 20% coconut fatty acids. The resultsobtained were similar to those reported in Examples 1 through 5.

EXAMPLE 7 The procedures of Examples 1 through 5 were repeated replacingthe sodium tallow soap of the compositions with an equal weight of asodium soap made with tallow fatty acids and 10% rosin acids. Theresults obtained were similar to those reported in Examples 1 through 5.

EXAMPLE 8 The procedures of Examples 1 through 7 were repeated in asimulated sea water prepared by adding 3.5 weight percent of sodiumchloride to city water. Results obtained were similar to those obtainedin Examples 1 through 7.

EXAMPLE 10 The sodium alkyl sulfate of Example 2 Composition G wasreplaced with the same quantity of the following in separate trials:sodium alkyl aryl sulfonate (sodium duodecyl benzene sulfonate), alkylaryl polyether alcohol 1 1 (isooctyl phenoxy polyethoxy ethanol-theethoxy being a 10 mol adduct of ethylene oxide) and an amphotericsurfactant. Typical examples of suitable amphoterics are sodiumN-coconut-fl-aminoproprionate and the Miranols of commerce, e.g.,

H, ("Miranol CM Cone.)

(Trademark of Mitanol Chemical 00.)

N CH: H l CHgCHzONa R- N I CHzC O O Na. H

where R represents the coconutderived alkyl. The procedures of Examples2 through 9 were repeated and results similar to those reported inExamples 2 through 9 were obtained.

EXAMPLE 11 upper limits of alkyl sulfate and free higher alcohol of thefirst embodiment of the present invention.

Composition A (Modified Example 7 of U.S. 2,527,075)

Weight percent Sodium tallow coconut soap (tallow to coconut ratio of75:25) 81.0 Sodium alkyl sulfate (alkyl coconut derived) 16.0 Freealcohol (coconut derived) 3.0

Composition A modified Example 7 of U.S. 2,527,075 by replacing thesodium salt of the sulfuric acid esters of coconut oil monoglyceride bysodium alkyl sulfate. Composition A represents approximately the lowerlimits of alkyl sulfate and free alcohol claimed by Preston.

The following Composition B represents the upper limits of alkyl sulfateand free alcohol of the present invention.

Composition B Weight percent Sodium tallow coconut soap 90.0 Sodiumalkyl sulfate 8.5 Free alcohol 1.5

Compositions A and B were compared for laundering effectivenessfollowing the procedure of Example 3 of this invention.

Composition A was found to foam very profusely in the rinse cycle anddid not rinse freely. The excessive foaming produced by Composition Aprolonged draining time of the suds produced in the sudsing and rinsingcycles. The odor of free alcohol was present during drying.

Use of Composition B yielded a cleaner wash and rinsed more freely thandid Composition A. Draining was more rapid following the suds cycle andin the rinse cycle. No odor of free alcohol was present during drying.

Preston (U.S. 2,527,075) teaches a use of at least 2% free alcohol andpreferably about free alcohol and a synthetic detergent content of atleast 16% by weight.

Washes performed using only 1.5% free alcohol and a synthetic detergentcontent of only 8.5% by weight yielded higher cleaning, freer rinsingand less residual odor than did the Preston compositions.

EXAMPLE l3 Composition A was prepared by adding the non-soap componentsof Example 1 Composition C and the nonsoap components of Example 2Composition G together and then adding the combined non-soap ingredientsto a sodium tallow coconut soap. In addition, several variations wereprepared (Compositions B, C and D).

Composition A Parts by weight Sodium alkyl sulfate (alkyl-coconutderived) 4.6 Free alcohol (coconut derived) 0.4 Sodium alkyl sulfate 2.0Sodium tripolyphosphate 4.0 Sodium chloride 6.0 Sodium tallow coconutsoap (tallow to coconut ratio to 20) 83.0

100.0 Composition B Parts by weight Sodium alkyl sulfate 4.6 Freealcohol 0.4 Isooctyl phenoxy polyethoxy alcohol (10 mol ethoxylate)(Triton X- trademark of Rohm & Haas) 2.0 Sodium tripolyphosphate 4.0Sodium sulfate 6.0 Sodium tallow coconut soap 83.0

100.0 Composition C Parts by weight Sodium alkyl sulfate 9.2 Freealcohol 0.8 Isooctyl phenoxy polyethoxy alcohol (10 mol ethoxylate) 2.0Sodium tripolyphosphate 2.0 Sodium sulfate 2.0 Sodium tallow coconutsoap 84.0

100.0 Composition D Parts by weight Sodium alkyl sulfate 4.6 Freealcohol 0.4 Isooctyl phenol polyethoxy alcohol (10 mol ethoxylate Sodiumtripolyphosphate 8.0 Sodium sulfate 12.0 Sodium tallow coconut soap 95.0

Compositions A, B, C and D were used in the Washing procedure of Example3. Cleaning results and overall performance were among the bestobtained. Composition D was rated highest of the 4 compositions. Sudsdrainage was rapid and no lime soap curds were evident.

All ingredients of compositions A or B or C or D may be blended togetherto yield a non-dusting powder or the mixture of the ingredients may beflaked or produced as a spray-dried bead by means well-known to the soapmaking art.

Tests made by replacing sodium tripolyphosphate by an equal quantity byweight of sodium hexametaphosphate or tetrasodium pyrophosphate incompositions A, B, C and D yielded similar results as above.

EXAMPLE 14 DishWashing compositions were made by dissolving 0.2 percentby weight of the following compositions in 100 p.p.m. hard water at F.

COMPOSITION A Parts by weight Sodium tallow coconut soap (tallow tococonut Composition A large selling commercial liquid dishwashingcompound All compositions were compared at 0.2% active ingredient levelin 120 F. city water containing 100 p.p.m. hardness. Soiled dishes,glasses and silverware were washed by hand by immersing the soiledarticles in the dishwashing solution and then removing adherent soilwith a dishcloth saturated with the dishwashing solution and allowingthe washed articles to air dry in a vertical position on a rack.

Compositions A and B were excellent soil removers. Composition C wasonly a fair soil remover and required repeated application of thedishcloth for complete soil removal.

Compositions A and B were high foamers. Composition C foamed soprofusely that a great deal of rinsing was required to eliminate foam.Compositions A and B were very free rinsing with lesser quantities ofrinse water.

A, B and C were all equally mild to skin even after repeated use.

EXAMPLE 0.2 percent by weight of Compositions A and B of Example 14 wereprepared in city Water of 100 p.p.m. hardness. /2 percent by weight ofsodium hypochlorite was added to the solutions maintained at 120 F.'Heavily stained parts of a coffee stained aluminum and stainless steelpercolator were immersed in the hypochlorite containing composition Aand B solutions. The parts were removed from the solution using rubbergloves to avoid barehandled contact with the hypochlorite and scrubbedwith a nylon bristled bottle brush to remove loosened soil and stainsand then rinsed in clear water and allowed to air dry. All coffee stainswere easily and completely removed. The dried aluminum and stainlesssteel coffee parts were completely clean, bright and spot and filmfree.

The same compositions with the added hypochlorite were effective inremoving soil of scorched oatmeal cheese fondues, bread doughs and bakedon carbon deposits from aluminum and stainless steel utensils.

By reducing the bleach content so as to yield composition solutionscontaining about a p.p.m. chlorine concentration, immersed fabrics orsolid dishes, silverware and cups and glasses may be effectivelysantized or disinfected.

l 4 EXAMPLE 16 Bar soaps were made from the following compositions.

Parts by weight Sodium tallow soap 95.0 Sodium alkyl sulfate 4.6 Freehigher alcohol 0.4

Parts by weight Sodium tallow soap 90.0 Sodium alkyl sulfate 8.5 Freehigher alcohol 1.5

The tallow soap was made from fatty acids of 42 C. titre. The alkylsulfate and free higher alcohol were derived from coconut oil. To sixtyparts of the composition in a stainless steel beaker was added 40 partsof 100 p.p.m. city water. The mixture was heated to 180 F. and handmixed with a spatula until a uniform and spreadable paste resulted. Thefluid paste was spread as a thin layer on a polyethylene sheet andallowed to air dry to a moisture content of 15 weight percent. The driedcomposition was broken into small flakes and fed to a grinder. Theextruded plastic-like ribbons from the grinder were pressed intorectangular molds and allowed to cool and harden.

The soap bars so formed were eifective hand cleaners, foamed well inboth hard and soft water and the foam produced was easily eliminated byrinsing without evidence of lime soap curd formation.

EXAMPLE 17 A composition comprised of Parts by weight Sodium tallow soap95.0 Sodium alkyl sulfate 4.6 Free higher alcohol 0.4

was dissolved in soft water (zero p.p.m. hardness) to yield a solutionof 0.2 weight percent concentration in water. A heavy and persistentfoam was generated in the glass container by vigorous shaking of theglass container. The copious adherent foam so produced was eliminatedonly after the use of much rinse water.

In another trial, sufiicient anhydrous calcium chloride was added to the0.2 weight percent solution in soft water to yield a solution containing50 p.p.m. hardness. A heavy and persistent foam was generated byshaking. The copious foam so produced was freely eliminated by the useof a much smaller quantity of rinse water.

No lime soap curds were observed in the trials using either soft or 50p.p.m. hard water. In this example a small amount of hardness isbeneficial over no hardness in the cleaning process using a soap-basedformulation.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

1. A composition consisting essentially of about to parts by weight ofsoap and about 5 to 10 parts by weight of an alkyl sulfate-free higheralcohol mixture, the free higher alcohol content of the alkylsulfate-free higher alcohol mixture being from 5 to 15 weight percent,said soap consisting of a sodium salt of essentially 8 to 18 numberedcarbon fatty acid, said alkyl sulfate being a sodium alkyl sulfate inwhich the alkyl portion consists essentially of 8 to 18 numbered carbonlengths and said free alcohols consisting essentially of 8 to 18numbered carbon monohydric alcohols.

2. A composition consisting essentially of about 76 to 95 parts byweight of a soap consisting of a sodium salt of essentially 8 to 18numbered carbon fatty acids, about to parts by weight of an alkylsulfate-free higher alcohol mixture, the free higher alcohol content ofthe alkyl sulfate-free higher alcohol mixture being from 5 to weightprecent, said alkyl sulfate being a sodium alkyl sulfate in which thealkyl portion consists essentially of 8 to 18 numbered carbon lengthsand said free alcohols consisting essentially of 8 to 18 numbered carbonmonohydric alcohols, about 2 to 4 parts by weight of a syntheticdetergent selected from the group consisting of linear alkyl arylsulfonates, alkyl sulfonates, alkyl aryl polyether sulfates andsulfonates, alkyl polyether alcohols, alkyl aryl polyether alcohols,sorbito, glycol and glyceryl esters of higher acids and fatty acid-aminecondensation amphoteric products, about 2 to 8 parts by weight of asodium salt of phosphoric acid, said sodium salt having sesquesteringproperties and being selected from the group consisting of sodiumtripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate andabout 2 to 12 parts by weight of an inorganic salt selected from thegroup consisting of sodium chloride and sodium sulfate.

3. A composition according to claim 1 consisting essentially of about 90to 92 parts by weight of a sodium tallow coconut soap, the ratio oftallow to coconut being 80 to 20, and about 8 to 10 parts by weight of asodium alkyl sulfate-free higher alcohol mixture, the free higheralcohol content of the sodium alkyl sulfate-free higher alcohol mixturebeing from 5 to 10 weight percent and said alkyl portion of the alkylsulfate and free higher alcohol being derived from coconut oil.

4. A composition according to claim 2 consisting essentially of about 80to 95 parts by weight of a sodium tallow coconut soap, the ratio oftallow to coconut being 80 to 20, about 5 parts by weight of a sodiumalkyl sulfate-free higher alcohol mixture, the free higher alcoholcontent of the alkyl sulfate-free higher alcohol mixture being 5 to 10weight percent, said alkyl portion of the alkyl sulfate and free higheralcohol being derived from coconut oil, about 2 to 4 parts by weight ofa nonionic detergent said detergent being an isooctyl phenoxy polyethoxyethanol containing 10 moles of ethylene oxide, about 4 to 8 parts byweight of sodium tripolyphosphate and about 6 to 12 parts by weight ofsodium sulfate.

5. A composition according to claim 2 in which the weight ratio betweensoap and synthetic detergents is at least 9 to 1.

6. A composition according to claim 1 in which at least 10 percent byweight of the soap is rosin soap.

7. A composition according to claim 2 in which at least 10 percent byweight of the soap is rosin soap.

8. A composition according to claim 5 in which at least 10 percent byweight of the soap is rosin soap.

References Cited UNITED STATES PATENTS 3,454,500 7/1969 Lancashire 252-2,588,264 3/1952 McDonald 252-121 2,567,645 9/1951 Limburg 252-1212,527,075 10/1950 Preston 252-121 2,502,881 4/1950 Parker 252-1092,437,253 3/1948 Henderson 252-109 2,388,767 11/1945 Safrin 252-1212,294,075 8/1942 Colgate 252-121 2,240,957 5/1941 Munz 252-121 X2,166,315 7/1939 Martin 252-550 2,046,242 6/ 1936 Bertsch 252-109FOREIGN PATENTS 201,233 3/1955 Australia 252-109 740,838 8/1966 Canada252-109 535,809 4/ 1941 Great Britain 252-109 LEON D. ROSDOL, PrimaryExaminer D. L. ALBRECHT, Assistant Examiner US. Cl. X.R.

